Phenyl isocyanate → HCID 13772020, compound

HRID 980889Notes

Reaction equation

HRID 980889 reaction equation
[C:1]1([N:7]=[C:8]=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([C:12]1[C:13]([NH2:25])=[C:14]([C:18]([O:23][CH3:24])=[C:19]([O:21][CH3:22])[CH:20]=1)[C:15]([OH:17])=O)C>N1C=CC=CC=1.[OH-].[Na+]>[CH3:24][O:23][C:18]1[C:19]([O:21][CH3:22])=[CH:20][CH:12]=[C:13]2[C:14]=1[C:15](=[O:17])[N:7]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:8](=[O:9])[NH:25]2

Participants

5

Reactant 2

HCID 7672Phenyl isocyanateHCID 20221217HCID 20221217, compound

Product 1

HCID 13772020HCID 13772020, compound

Reagents, catalysts & solvents 2

HCID 1049PyridineSolvent2×HCID 14798Sodium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

To phenyl isocyanate (2.26 ml, 2.48 g, 20.8 mM) in pyridine (9.2 ml) at 0° C. was added a cold solution of ethyl 2-amino-5,6-dimethoxybenzoic acid (3.0 g, 13.3 mM) in pyridine (16.7 ml). The solution was stirred at 0° C. for thirty minutes, then kept at room temperature for one hour. The solution was then concentrated to dryness to give a white solid. This was dissolved in 69.9 ml of 1N NaOH (4:1 MeOH-H2O) and heated at reflux for two hours. The solvent was removed in vacuo and the gummy residue partially dissolved in H2O (100 ml). The mixture was taken to pH 6 with acetic acid and the resulting white solid filtered, washed well with H2O (50 ml) and dried to afford crude product as a white solid; 4.13 g, mp 215°-225° C. (softens 190° C.). Recrystallization from isopropanol (250 ml) afforded the title compound as a white solid; 2.65 g (65.8%); mp 241°-243° C. CF3COOH(TMS) 7.10-7.80 (m, 7H, 7-H, 8-H, 9-H, 10-H, 11-H, 12-H, 13-H), 4.05 (s, 3H, 5 or 6-OCH3), 10 (s, 3H, 5 or 6-OCH3). M+ 298.

Workup

  1. concentrationThe solution was then concentrated to dryness
  2. customto give a white solid
  3. temperatureheated
  4. temperatureat reflux for two hours
  5. customThe solvent was removed in vacuo
  6. dissolutionthe gummy residue partially dissolved in H2O (100 ml)
  7. filtrationthe resulting white solid filtered
  8. washwashed well with H2O (50 ml)
  9. customdried
  10. customto afford crude product as a white solid
  11. custom4.13 g, mp 215°-225° C. (softens 190° C.)
  12. customRecrystallization from isopropanol (250 ml)

Sources & evidence

ORD record
ord-9a21699fd32b44e7add47dbd2404efc7
Source dataset
uspto-grants-1987_01
Patent number
US04639518

Reaction notes

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